Exploration of Metal-Molecule interaction of subnanometric heterogeneous catalysts via simulated Raman spectrum
Exploration of Metal-Molecule interaction of subnanometric heterogeneous catalysts via simulated Raman spectrum
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通过模拟拉曼光谱探索亚纳米多相催化剂的金属-分子相互作用
DOI：
10.1016/j.apsusc.2021.152194
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发表时间：
2021-12
影响因子：
6.7
通讯作者：
Liu Xingchen
中科院分区：
文献类型：
--
作者：
Xu Yuxing;Li Bei;Zhang Jiafei;Bai Ge;Zhang Xiaolong;Hao Qinglan;Wang Yahao;Zhou Xiaoshun;Teng Botao;Liu Xingchen
到目前为止，使用最先进的直接图像或间接光谱技术，以同时确定非均相催化剂的表面精细结构，并预测在操作条件下的表面物种的化学状态，特别是到亚纳米级，甚至原子级，仍然是一个重大的挑战。然而，将非均相催化剂的尺寸从本体减小到原子水平，负责金属和吸附的分子之间的独特相互作用的光谱特性将因此被调谐，从而引起即使相同金属/分子组合的非相干光谱特性，如文献中反复证明的。本工作详细介绍了一种新的化学策略，以确定来自亚纳米团簇，甚至单原子催化剂在反应气氛下，一个长期存在的问题，阻碍了进一步实施的拉曼技术在微型多相催化拉曼光谱的纠缠特性。我们通过使用密度泛函理论（DFT）方法模拟三种典型Ptx/CeO 2的拉曼光谱来说明这一概念（x = 1，2，9）分别代表孤立原子、层状团簇和多层团簇的尺寸增大的系统，在CO气氛下获得光谱特性，在相关的实验研究中，通常被来自不可避免的CO/Pt相互作用的多种干扰所掩盖。本论文所探索的新方法为理论化学方法作为一种通用工具，在识别复杂化学环境中多种干扰所掩盖的内在光谱特征方面，补充现有的实验方法开辟了一条新的途径。
To date, using either state-of-the-art direct image or indirect spectroscopic techniques to simultaneously identify the surface fine structure of heterogeneous catalyst and predict the chemical state of surface species under operando conditions, particularly down to subnanometry and even atomic scale, remains a substantial challenge. Nevertheless, reducing the size of the heterogeneous catalyst from bulk down to atomic level, the spectroscopic characteristics responsible for the unique interaction between metal and adsorbed molecules will thereby be tuned, giving rise to non-coherent spectroscopic characteristics for even the same metal/molecule combination, as repeatedly witnessed in literatures. This work details a new chemical strategy to identify the tangling characteristics of Raman spectra derived from the subnanometric cluster and even single atom catalysts under reactive atmosphere, a long-standing issue that impeded the further implementation of Raman techniques in miniaturized heterogeneous catalysis. We illustrate this concept through the use of a density functional theory (DFT) approach to simulate the Raman spectra of three typical Ptx/CeO2(x = 1, 2, 9) systems of increasing sizes which represent isolated atom, layered clusters, and multiple layer clusters, respectively, under CO atmosphere to acquire the spectroscopic characteristics, usually masked by multiple interferences from the inevitable CO/Pt interaction circulated in relevant experimental studies. The novel approach explored in this manuscript should open up a new avenue for the use of theoretical chemistry method as a general tool to complement the current experimental method in identifying the intrinsic spectroscopic features masked by multiple interferences originated from complex chemical environment.
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影响因子：
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作者：
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DOI：
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期刊：
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影响因子：
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作者：
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